Reflecting spherical microcapsules and methods of their production

ABSTRACT

Spherical microcapsules including light reflecting solid integral particles reflecting incoming light in a defined direction for determining the position and orientation of the microcapsule are produced by preparing a first liquid phase containing a first polymerization partner; preparing a second liquid phase containing a second polymerization partner, the first liquid phase not being soluble in the second liquid phase, and the second polymerization partner being configured to polymerize with the first polymerization partner under polymerization conditions; dispersing the solid particles in the first liquid phase; forming droplets of the first liquid phase including at least one solid particle; and immersing the droplets in the second liquid phase under the polymerization conditions. The first polymerization partner and the second polymerization partner polymerize at the surfaces of the droplets forming shells of a polymeric material enclosing the individual droplets, and the light reflecting solid integral particles are fixed to the shells.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of International ApplicationPCT/EP2015/075441 with an International Filing Date of Nov. 2, 2015 andclaiming priority to European Patent Application No. 14 191 390.5entitled “Reflecting Spherical Microcapsules and Methods of theirProduction”, filed on Nov. 1, 2014.

FIELD OF THE INVENTION

The present invention relates to a method of producing sphericalmicrocapsules including light reflecting solid integral particles.Further, the present invention relates to a plurality of such sphericalmicrocapsules for seeding an essentially transparent fluid to trackmovements of the fluid both in translational and rotational directions.

BACKGROUND OF THE INVENTION

In a conference talk on “Direct Optical Vorticity Probing”, 14^(th)European Turbulence Conference, Sep. 1-4, 2013, Lyon, France, theinventors disclosed microcapsules for seeding a liquid fluid to tracktranslational and rotational movements of the fluid. The microcapsulesare transparent, neutrally buoyant, spherical, and with a glass mirrorencapsulated inside. On average, the microcapsules have a diameter of 70μm. The refraction index is 1.334, almost the same as the refractionindex of water. No further details of the microcapsules, however, weregiven.

In another talk “Vorticity Measurements in Taylor-Couette Flows”presented on the 66th Annual Meeting of APS DFD, Nov. 24-26, 2013,Pittsburgh, USA, the inventors indicated that the microcapsulescomprising the features as indicated above were prepared using amicro-fluidic device in that droplets of a first liquid phase includingthe micro-sized mirrors are dispensed into a flow of a second liquidphase. No further details were given.

M. B. Frish and W. W. Webb, “Direct Measurement of Vorticity by OpticalProbe”, Journal of Fluid Mechanics 107, 173-200 (1981) measured therotation rate of single micro-sized beads to obtain the vorticity of afluid seeded with the beads. The micro-sized beads were made of atransparent material and encapsulated flat mirror discs.

For the purpose of tracking both translational and rotational movementsof a fluid seeded with microcapsules including micro-mirrors, it isimportant that the microcapsules are small and spherical so that theydirectly follow the fluid, and that only their micro-mirrors reflectlight used for determining the position and orientation of themicrocapsules, i.e. that this light is not deflected by the materialencapsulating the micro-mirrors.

EP 0 484 546 A1 discloses a microcapsule and a method of making thesame. The microcapsule contains core substances enveloped by a capsulefilm obtained by coagulating fine colloidal particles with anelectrolyte. The capsule film is formed, through the use of electrolyte,by coagulating the materials of the film which consist of fine inorganicand/or organic colloidal particles. The method comprises adding asubstance to be encapsulated to a dispersion (hydrosol) of finecolloidal particles in which water is used as dispersion medium,dispersing said dispersion in an oil medium to form an emulsion, andcoagulating the fine colloidal particles in said emulsion by using anelectrolyte. In case the substance to be encapsulated is a water-solublematerial, it may simply be mixed in the hydrosol. The substance to beencapsulated may be a dye, pigment, medicine, agricultural chemical,perfume, synthetic material, adhesive, enzyme, bacterial cell, etc.

Ingmar Polenz et al.: “Controlling the Morphology of PolyureaMicrocapsules Using Microfluidics”, LANGMUIR, vol. 30, no. 44, Oct. 16,2014, pages 13405-13410 discloses the use of microfluidics tocontinuously produce mono disperse polyurea microcapsules having eitheraqueous or non-aqueous cores. The microcapsule shells are formed by thereaction between an isocyanate, dissolved in oil, and an amine,dissolved in water, at the surface of oil-in-water or water-in-oil dropsimmediately as they are formed. Different microcapsule morphologies canbe generated by using this approach. The thickness of the microcapsuleshell increases with an increases in the amine solubility in the oilallowing for controlling the shell thickness in a range from tens ofnanometers to several micrometers. These microcapsules are provided forapplications requiring the encapsulation, delivery, and release ofactive materials, such as self-healing materials, catalysts,agricultural chemicals, textile chemicals, and chemicals used in papermanufacturing.

US 2012/0129742 A1 discloses microcapsules including a core containingone or more alkali metal borates, optionally hydrated, dispersed in oneor more lubricating base oils of mineral, synthetic or natural origin,and a polymer shell.

US 2012/0003285 A1 discloses a method for manufacturing capsule series.The method includes separately conveying a first liquid solutioncontaining a first material and a second liquid solution containing aliquid polyelectrolyte. A series of drops is formed at an outlet, eachdrop including a central core formed from the first solution and aperipheral film formed from the second solution. Each drop is immersedin a gelling solution containing a reagent capable of reacting with thepolyelectrolyte of the film so as to form the gelled casing. The secondsolution contains at least one surfactant before the former contacts thefirst solution.

There still is a need of a method of producing spherical microcapsulesincluding light reflecting solid integral particles and a plurality ofspherical microcapsules for seeding an essentially transparent fluid totrack movements of the fluid both in translational and rotationaldirections producible by the method, which ensure that the microcapsulesfollow the flow translation and rotation faithfully and which allow forprecisely determining the position and the orientation of the sphericalmicrocapsules using light reflected by their solid integral particles.

SUMMARY OF THE INVENTION

The present invention provides a method of producing sphericalmicrocapsules including light reflecting solid integral particlesreflecting incoming light to be reflected by the solid integralparticles in a defined direction for determining the position andorientation of the microcapsule. The method comprises the steps ofpreparing a first liquid phase containing a first polymerizationpartner; preparing a second liquid phase containing a secondpolymerization partner, the first liquid phase not being soluble in thesecond liquid phase, and the second polymerization partner beingconfigured to polymerize with the first polymerization partner underpolymerization conditions; dispersing the solid integral particles inthe first liquid phase; forming droplets of the first liquid phaseincluding at least one of the solid integral particles; immersing thedroplets in the second liquid phase under the polymerization conditions,wherein the first polymerization partner and the second polymerizationpartner polymerize at the surfaces of the droplets forming shells of apolymeric material enclosing the individual droplets; and fixing thelight reflecting solid integral particles to the shells.

Further, the present invention provides a plurality of sphericalmicrocapsules for seeding a transparent fluid to track movements of thefluid both in translational and rotational directions. Each microcapsulecomprises a core; a shell of a polymeric material enclosing the core;and at least one light reflecting solid integral particle reflectingincoming light to be reflected by the at least one solid integralparticle in a defined direction for determining the position andorientation of the microcapsule, embedded in the core and fixed in itsorientation with regard to the shell. The shell and the core aretransparent for the light to be reflected by the at least one solidintegral particle entering and exiting the microcapsule. The shell is sothin that it does essentially not deflect the light to be reflected bythe at least one solid integral particle entering and exiting themicrocapsule, and the core includes a main component of the fluid suchthat a refraction index of the core essentially matches a refractionindex of the fluid.

Other features and advantages of the present invention will becomeapparent to one with skill in the art upon examination of the followingdrawings and the detailed description. It is intended that all suchadditional features and advantages be included herein within the scopeof the present invention, as defined by the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention can be better understood with reference to the followingdrawings. The components in the drawings are not necessarily to scale,emphasis instead being placed upon clearly illustrating the principlesof the present invention. In the drawings, like reference numeralsdesignate corresponding parts throughout the several views.

FIG. 1 illustrates a single reflecting spherical microcapsule accordingto the present invention dispersed in a fluid.

FIG. 2 is a block diagram illustrating the steps of the method ofproducing microcapsules according to the present invention.

FIG. 3 illustrates an ultrasound spray device for producing themicrocapsules according to the present invention; and

FIG. 4 illustrates a microfluidic device for producing the microcapsulesaccording to the present invention.

DETAILED DESRIPTION

In the method of producing spherical microcapsules including solidintegral particles reflecting incoming light to be reflected in adefined direction according to the present invention, a first liquidphase containing a first polymerization partner and a second liquidphase containing a second polymerization partner are prepared. The firstand the second liquid phase differ in that at least a base component ofthe first liquid phase is not soluble in a base component of the secondliquid phase. The first and second polymerization partners are selectedsuch that the second polymerization partner polymerizes with the firstpolymerization partner under polymerization conditions. The term“polymerization partner”, however, here also includes a catalyst, i.e.one of the polymerization partners may not become part a polymericmaterial resulting from the polymerization of the first and secondpolymerization partners but only catalyze the polymerization of theother polymerization partner. Further, a catalyst may also be present inthe first and/or second liquid phase in addition to the first or secondpolymerization partner, respectively. The solid particles are selectedfrom any light reflecting particles reflecting the incoming light to bereflected in the defined direction for determining the position andorientation of the microcapsule. Particularly, they may bemicro-mirrors. They may, however, also be or include diffractiongratings. The solid particles are dispersed in the first liquid phase.From this dispersion of the solid integral particles in the first liquidphase, droplets are formed which include at least one of the solidparticles. The formation of the droplets may result in some droplets notincluding any solid particle which may be discarded or not. Theformation of the droplets may further result in droplets including one,two or more solid integral particles which may be separated or not. Thedroplets are then immersed in the second liquid phase under thepolymerization conditions. This results in the first polymerizationpartner and the second polymerization partner polymerizing at thesurfaces of the droplets and thus forming shells of a polymeric materialenclosing the individual droplets. A polymerization taking place at aninterface of two liquid phases each containing one of the polymerizationpartners is generally known and called interfacial polymerization. Forexample, interfacial polymerization is used for producing polyanilinenanofibers, see Jiaxing Huang et al. “Polyaniline nanofibers: facilesynthesis and chemical sensors”, J. Am. Chem. Soc. 125 (2):314-5,January 2003. In the method of the present invention, the shells formedby interfacial polymerization and enclosing the droplets may be made sothin that they do not deflect light. By appropriately selecting thepolymerization partners the shells will nevertheless be durable. Thedroplets including the solid particles and enclosed by the shells arethe desired spherical microcapsules. The spherical shape of themicrocapsules may be enhanced by adding a surfactant to the first liquidphase and/or to the second liquid phase.

Preferably, the average number of solid integral particles permicrocapsule is between 1 and 5, more preferably, it is between 1 and 3,even more preferably it is between 1 and 2. Typically, the yield ofspherical microcapsules including at least one solid integral particleas compared to the entire number of spherical microcapsules produced inthe method according o the present invention is 60% to 95%; often it isbetween 89% and 90%.

The size of the solid integral particles is typically between 5 μm and100 μm; and often it is between 5 μm and 50 μm, or between a quarter andthree quarters of the diameter of the microcapsules.

The light to be reflected may be any light, particularly visible lightbut also including infrared and ultra-violet light, that is usable intracking movements of fluids both in translational and rotationaldirections by being reflected by small particles.

Usually, the microcapsules will not be used as probes for trackingmovements of the second liquid phase because the first liquid phase notbeing soluble in the second liquid phase typically has a quite differentrefraction index as compared to the second liquid phase. Thus, themethod of the present invention will usually further include collectingthe droplets enclosed by the shells from the second liquid phase anddispersing the droplets enclosed by the shells in a third liquid phase.The third liquid phase may particularly have a base component identicalto the base component of the first liquid phase. If the third liquidphase has a refraction index essentially matching the refraction indexof the first liquid phase, the microcapsules are very well suited fortracking translational and rotational movements of the third liquidphase using light reflected by their solid particles, as this light isnot deflected at the interface of the microcapsules.

Particularly, the first liquid phase may be soluble in the third liquidphase. Even more particular, the third liquid phase may be water or anaqueous solution, and the first liquid phase may be an aqueous solutionincluding a hydrogel. On the other hand, the second liquid phase may bean oleaginous, i.e. an oil based or oily, phase.

In another embodiment of the method of the present invention, however,the first and third liquid phases may be oleaginous phases whereas thesecond liquid phase is an aqueous solution. In this embodiment theoleaginous first liquid phase may include a organogel or any other gelentrapping oil.

Examples of suitable organogels include cross-linked polybutadienes,polyacrylates, polystyrenes, polyureas that are formed from formaldehydederivatives, polyisoprene derivatives (and their cross-linked productsusing colloidal sulfur) and polysiloxanes. More particular examples ofsuitable organogeles are disclosed in U.S. Pat. No. 5,298,258 A “Acrylicoily gel bioadhesive material and acrylic oil gel preparation”.

In any case, the first liquid phase in the cores of the sphericalmicrocapsules, whose composition differs from that one the polymericmaterial of the shells may also polymerize or otherwise solidify.Particularly, the first liquid phase may gel or solidify at temperaturesbelow a gelling or solidification temperature. This gelling orsolidification temperature may be below a temperature included in thepolymerization conditions. Then, the gelling or solidification onlytakes place after the shells enclosing the droplets are formed whencooling down the microcapsules.

The gelling or solidification of the first liquid phase fixes the solidparticles reflecting the light within the microcapsules, i.e. to theirshells. This ensures that any translational or rotational movement ofthe microcapsules is directly transferred onto their light reflectingsolid integral particles and may thus be determined using the lightreflected by the solid integral particles. If the first liquid phaseused for producing the microcapsules does not gel or solidify, it may benecessary to fix the light reflecting particles to the shells of themicrocapsules in some other way, like, for example, by polymeric chains.

If the gelling or solidification temperature of the first liquid phaseis higher than a use temperature of the microcapsules, which may, forexample, be room temperature, the solid integral particles of themicrocapsules will always be fixed to their shells when using themicrocapsules for probing the vorticity of a fluid, for example.

One of the first and second polymerization partners contained in thefirst and second liquid phases may be an amine, whereas the other of thefirst and second polymerization partners may be an isocyanate compound.If the first liquid phase is aqueous solution, whereas the second liquidphase is an oleaginous phase, the amine will be the first polymerizationpartner in the first liquid phase, whereas the isocyanate compound willbe the second polymerization partner in the second liquid phase as theamine is soluble in water whereas the isocyanate is soluble in oil.

In a more particular embodiment of the method of the present invention,the droplets of the first liquid phase including the solid particles areformed by feeding the dispersion of the solid particles in the firstliquid phase through an ultrasound spray nozzle into a gaseous phase.Out of the gaseous phase, the droplets may then fall into the secondliquid phase. This corresponds to ultrasonic mediated spray depositionof the droplets through the gaseous phase into the second liquid phase.

In another more particular embodiment of the method of the presentinvention, the droplets are formed of the first liquid phase includingthe solid particles and immersed in the second liquid phase within amicro-fluidic device. A clog-free production of the microcapsules isachieved in that the first liquid phase is first fed into a flow of afourth liquid phase not yet including the second polymerization partnerto form the droplets, before adding the second polymerization partner toprepare the second liquid phase including the fourth liquid phase. Here,the first liquid phase will also not be soluble in the fourth liquidphase, and the second polymerization partner may be added to the fourthliquid phase dissolved in a liquid carrier. The usage of the fourthliquid phase not yet including the second polymerization partner ensuresthe formulation of separate droplets fully immersed or emulsified in thefourth liquid phase before the polymerization is started by adding thesecond polymerization partner. This ensures that the polymerization doesnot result into bonds between individual droplets or between individualdroplets and the walls of the microfluidic device clogging themicrofluidic device.

Both more particular embodiment of the method of the present inventionmay be used to produce monodisperse microcapsules, i.e. a pluralitymicrocapsules of a same diameter. Such monodisperse microcapsules haveidentical flow properties, i.e. they follow a flow of a fluid seededwith the microcapsules in an identical way.

In a plurality of spherical microcapsules for seeding an essentiallytransparent fluid to track movements of the fluid both in translationaland rotational directions according to the present invention, eachmicrocapsule comprises a core, a shell of a polymeric material enclosingthe core, and at least one light reflecting solid integral particlereflecting incoming light to be reflected in a defined direction fordetermining the position and orientation of the microcapsule, embeddedin the core and fixed to the shell. The shell and the core areessentially transparent for light to be reflected by the at least onesolid integral particle and the light reflected by the at least onesolid integral particle used for determining the position andorientation of the individual microcapsule, i.e. for the light enteringand exiting the microcapsule. This is achieved in that the shell is sothin that it does essentially not deflect the light entering and exitingthe microcapsule, and in that the core includes a main component of thefluid such that a refraction index of the core essentially matches arefraction index of the fluid. Essentially matching refraction indicesmay differ by a few percent. Due to the small diameter of themicrospheres, these small differences in refraction index will notresult in a relevant defection of the light entering and exiting themicrocapsules.

In the terms “essentially transparent” and “does essentially notdeflect”, the word “essentially”, is used to indicate that the light ispredominantly transmitted or not deflected, respectively. For example,the intensity of the light to be reflected may be reduced by up to about40%. Preferably, however, it is not reduced by more than 20%, morepreferably it is not reduced by more than 10% and most preferably it isnot reduced by more than 5% when passing through one of the sphericalmicrocapsules, either directly or reflected by one of its lightreflecting solid integral particles.

In the spherical microcapsules according to the present invention, theshells ensure the structural integrity in that they inhibit that thecore dissolves in the fluid seeded with the microcapsules. Further, thepolymeric shell ensures the spherical shape of the microcapsules evenunder shearing forces acting upon the microcapsules. In this regard,they may allow for the main component of the fluid passing the shell andentering into the core to build up some osmotic pressure within thecore. The shape of the microcapsules may also be stabilized by gellingor solidification of the core. Gelling or solidification of the corewill also fix the solid particle embedded in the core to the shell ofthe microcapsule.

The polymeric material of the shell will typically have a differentrefraction index as compared to the fluid and the core of themicrocapsules. It will nevertheless not deflect the light to bereflected by the solid integral particle as long as it is not thickerthan the wavelength of this light. Preferably, the polymeric material ofthe shell is even thinner than the wavelength of this light. Morepreferably, its thickness is not more than half of the wavelength ofthis light. Most preferably, it is about a quarter of the wavelength ofthe light. Wth such a thin shell, the light will not be deflected at theinterfaces between the fluid and the shell, and between the shell andthe core even with some difference in refraction index between the shelland the core and/or the fluid. In absolute terms, the thickness of thepolymeric material of the shell may be in a range from 100 nm to 250 nm.

Preferably, the microcapsules according to the present invention aremonodisperse. They will have a minimum diameter of about 10 μm to ensurethat the embedded light reflecting solid particles are usable fordetermining position and orientation of the microcapsules from the lightreflected by them. The diameter of the microcapsules may be up to about200 μm. Preferably, however, it is smaller than 100 μm. Microcapsuleshaving a diameter in a range of 10 μm to 70 μm will perfectly followmost fluids for tracking their vorticity.

Referring now in greater detail to the drawings, FIG. 1 shows amicrocapsule 1 dispersed in a fluid 2. The microcapsule consists of acore 3, a shell 4 enclosing the core 3, and a micro-mirror 5 embedded inthe core 3. The core 3, besides the micro-mirror 5, consists of ahydrogel that is gelled at a use temperature of the microcapsule 1. Thehydrogel consists of a polymeric component and water. The gelledhydrogel fixes the orientation of the micro-mirror 5 in the microcapsule1, i.e. every movement of the shell 4 due to any translational orrotational movement of the fluid 2 is transferred to the micro-mirror 5.The micro-mirror 5 is provided in the microcapsule 1 to reflect lightand to allow for determining the position and orientation of themicrocapsule 1 within the fluid 2 due to the direction into which thelight coming out of defined direction is reflected. To not disturb thisdetermination of the position and orientation of the microcapsule 1 byany deflection of the light, a refraction index of the core 3, i.e. ofthe hydrogel, matches a refraction index of the fluid 2 which is anaqueous solution, i.e. which has the same base component water as thecore 3. The shell 4 does not deflect the light, because its thickness isonly about a quarter of a wavelength of the light. As a result, theshell 4 is basically invisible to the light. It is to be understood thatthe fluid 2, the shell 4 and the core 3 have to be transparent todetermine the position and orientation of the microcapsule due to lightreflected by the micro-mirror 5 and that the micro-mirror 5 has to beplane. Instead of a plane micro-mirror 5, however, another solidparticle reflecting incoming light in a defined direction could beembedded in the core 3. This other particle could, for example, be adiffraction grating. The shell 4 is made of a polymeric material throughwhich water may pass to a limited extent like through a semipermeablemembrane. The amount of water which may pass through the shell 4 will,however, be limited by the resulting osmotic pressure in the core 3. Forexample, the shell 4 may consist of an isocyanate-based polymer which isof high toughness and elasticity even at the low thickness.Particularly, this thickness may be in the order of several tennanometers, i.e. of less than half the wavelength of visible light. Theactual thickness of the shell 4 may be adjusted by appropriatelyselecting its components and the conditions under which the microcapsule1 is produced of the shell 4. Instead of a hydrogel in the core 3 and anaqueous solution or water as the fluid 2, both the core 3 and the fluid2 may comprise an oil as their base component. In this case, therefraction index of the core 3 is also matched to the refraction indexof the fluid 2.

In another embodiment of the microcapsule 1, the core 3, besides themicro-mirror 5, consists of an organogel entrapping a oleaginous liquidphase and gelled at the use temperature of the microcapsule 1. Here, thegelled organogel fixes the orientation of the micro-mirror 5 in themicrocapsule 1, and a refraction index of the core 3, i.e. of theorganogel, matches a refraction index of the fluid 2 which is anoleaginous solution, i.e. which has the same oily base component as thecore 3.

According to the present invention, the microcapsule 1 according to FIG.1 is prepared as illustrated in FIG. 2. In step 6, a first liquid phaseis prepared. This liquid phase will later form the core 3 of themicrocapsule 1. Further, it includes a first polymerization partnersoluble in the liquid phase. In step 7, reflecting particles like themicro-mirror 5 are dispersed in the first liquid phase. In step 8,droplets are formed of the dispersion formed in step 7 with the aim toinclude at least one reflecting particle in each droplet. In step 9,these droplets are immersed in a second liquid phase which is preparedin step 10. The second liquid phase contains a second polymerizationpartner which, upon immersing the droplets in the second liquid phase,together with the first polymerization partner contained in the firstliquid phase forms the shell 4 of the microcapsule 1 by interfacialpolymerization. The first liquid phase is not soluble in the secondliquid phase. Instead, it is preferred to have a considerableinterfacial surface tension ensuring a spherical shape of themicrocapsules. As a result, however, there will be a considerabledifference in refraction indices between the first and second liquidphases, i.e. the second liquid phase may not be the fluid 2 according toFIG. 1. Therefore, in step 11, the microcapsules are collected orseparated from the second liquid phase, and in step 12 they aredispersed in the fluid 2 or a liquid of similar composition.

FIG. 3 illustrates an ultrasonic spray deposition device 13 forproducing the microcapsules 1 according to the present invention. In amixing container 14 the light reflecting particles 15 are dispersed inthe first liquid phase 16. A syringe-styled pump 17 feeds the dispersion18 formed in the mixing container 14 to a spray nozzle 19 subject toultrasound 20 generated by an ultrasound generator 21. The dispersion 18exiting the spray nozzle 19 is disrupted into the droplets 22 which fallinto a basin 23 containing the second liquid phase 24. As soon as thedroplets 22 are immersed in the second liquid phase 24, themicrocapsules 1 are formed. With appropriately selected components andconditions of production, the microcapsules will directly bemonodisperse, or they will be of such different diameter, because thebigger microspheres are due to an agglomeration of two or more initialdroplets 22, that a monodisperse plurality of microcapsules may easilybe separated. This first liquid phase may only be liquid when heated upto a temperature above room temperature so that the core 3 of themicrocapsules 1 gels or solidifies when getting down to roomtemperature. The microcapsules 1 produced by the ultrasonic spraydeposition device 13 according to FIG. 3 have a typical diameter of15-60 μm with an average size of about 40 μm. The first polymerizationpartner contained in the first liquid phase 16 may be an amine, whereasthe second polymerization partner included in the second liquid phase 24may be an isocyanate compound, i.e. a very reactive polymerizationpartner which quickly reacts with the amine in the first liquid phase 16to form the shells 4 of a polymeric material by interfacialpolymerization.

FIG. 4 depicts a microfluidic device 25 which may alternatively be usedfor producing the microcapsules according to the present invention. Themicrofluidic device 25 may, for example, be fabricated by standardmethods using soft lithography, see for example Y. N. Xia, G. M.Whitesides, Abstr. Pap. Am. Chem. Soc. 1997, 214, 348. In one example ofusing the microfluidic device 25 for producing the microcapsulesaccording to the present invention, the first liquid phase 16 is a 5% byweight gelatin solution (Bovine Skin, Sigma Aldrich) supplemented with0.5% by weight polyethyleneimine (PEI, Sigma Aldrich) as the firstpolymerization partner. In this first liquid phase 16, 0.5% by weightglitter flakes (Ho Long Glitter Enterprises Co., average size 20 μm) aredispersed as micro-mirrors. The resulting dispersion 18 is dispersed inan oleaginous solution 26 consisting of kmc oil (isomer mixture ofdisopropylnaphthalene). By means of homogeneous shearing at a T-junction27 of the microfluidic device 25, a continuous rip-off of droplets 22 isachieved resulting in the production of a monodisperse droplet emulsion28. The emulsion 28 flows into a V-junction 29 where a furtheroleaginous solution 30 composed of 0.1% by weight Pluronics P123 (SigmaAldrich) and 5% by weight 2.4-toluene diisocyanate (TDI, Sigma Aldrich)that are dissolved in kmc oil is fed. In combination, the oleaginoussolutions 26 and 30 form the second liquid phase 24. After theV-junction 29, the TDI in the second liquid phase 24 reacts with the PEIto form the shells enclosing the droplets 22 to form monodispersemicrocapsules 1. The microcapsules 1 are then purified and transferredinto an aqueous phase by decanting the capsules with tetrahydrofuran(THF) for several times to get rid of residual surfactant (P123) andunreacted TDI, and transferring the highly concentrated suspension intoan aqueous surfactant (P123) solution. Under these conditions themicrocapsules are longtime stable for several months. The details of thecompositions of the materials and the figures indicated here allow forworking the present invention. They are, however, not critical to thepresent invention.

Both the ultrasonic method illustrated in FIG. 2 and the microfluidicmethod illustrated in FIG. 4 produce spherical microcapsules includinglight reflecting solid integral particles according to the presentinvention. In an example of the ultrasonic method, 89% of the producedspherical microcapsules included at least one light reflecting solidintegral particle, and the average number of light reflecting solidintegral particles per spherical microcapsule was 1.6. In an example ofthe microfluidic method, 81% of the produced spherical microcapsulesincluded at least one light reflecting solid integral particle, and theaverage number of light reflecting solid integral particles perspherical microcapsule was 3.3.

An example of the light reflecting particles to be used in the sphericalmicrocapsules are TiO₂ coated SiO₂ snippets of irregular shape that arecommonly used in decoration industry and in care materials. A typicalparticle size distribution of the light reflecting particles used withinthe above examples extends from above 5 μm to about 40 μm, the maximumdimension of most of the particles being smaller than 20 μm with.

The shell thicknesses of the spherical microcapsules produced were in atypical range of 100 nm to 250 nm.

With a concentration of the gelatin in the spherical microcapsulesincreasing from 2.5% to 10% by weight, their transparency for visiblelight provided by a halogen lamp dropped from 96% to 59% with stillbeing at 86% with 5% by weight gelatin. The transparency was determinedfrom an average brightness of bright light microscopic images of severalspherical microcapsules taken with a digital camera sensitive forvisible light as compared to the background brightness of the images.

Many variations and modifications may be made to the preferredembodiments of the invention without departing substantially from thespirit and principles of the invention. All such modifications andvariations are intended to be included herein within the scope of thepresent invention, as defined by the following claims.

We claim:
 1. A method of producing monodisperse spherical microcapsulescomprising a shell and a core, the method comprising: preparing a firstliquid phase containing a first polymerization partner; preparing asecond liquid phase containing a second polymerization partner, thefirst liquid phase not being soluble in the second liquid phase, and thesecond polymerization partner being configured to polymerize with thefirst polymerization partner under interfacial polymerizationconditions; dispersing light reflecting solid integral particles in thefirst liquid phase; forming droplets of the first liquid phase includingat least one of the light reflecting solid integral particles; immersingthe droplets in the second liquid phase under the interfacialpolymerization conditions, wherein the first polymerization partner andthe second polymerization partner polymerize at the surfaces of thedroplets forming shells of a polymeric material enclosing the individualdroplets; and fixing the light reflecting solid integral particles tothe shells; thereby producing monodisperse spherical microcapsulescomprising the core and the shell; wherein the core comprises 1 to 5light reflecting solid integral particles per microcapsule; and whereinthe shell comprises the polymeric material.
 2. The method of claim 1,further comprising collecting the droplets enclosed by the shells fromthe second liquid phase and dispersing the droplets enclosed by theshells in a third liquid phase, the third liquid phase having arefraction index essentially matching a refraction index of the firstliquid phase.
 3. The method of claim 2, wherein the first liquid phaseis soluble in the third liquid phase.
 4. The method of claim 2, whereinthe third liquid phase is water or an aqueous solution.
 5. The method ofclaim 1, wherein one of the first and second liquid phases is an aqueousphase, whereas the other of the first and second liquid phases is anoleaginous phase.
 6. The method of claim 1, wherein the first liquidphase is an aqueous solution including a hydrogel, or an oleaginoussolution including an organogel.
 7. The method of claim 1, wherein thefirst liquid phase gels or solidifies at temperatures below a gelling orsolidification temperature, the polymerization conditions including atemperature above the gelling or solidification temperature.
 8. Themethod of claim 7, wherein the gelling or solidification temperature ishigher than a use temperature of the microcapsules.
 9. The method ofclaim 1, wherein first liquid phase or the gelled or solidified firstliquid phase is transparent for the light to be reflected by the lightreflecting solid integral particles.
 10. The method of claim 1, whereinone of the first and second polymerization partners is an amine, and theother of the first and second polymerization partners is an isocyanatecompound.
 11. The method of claim 1, wherein the droplets are formed byfeeding the first liquid phase including the light reflecting solidintegral particles through a spray nozzle into a gaseous phase.
 12. Themethod of claim 1, wherein the droplets are formed of the first liquidphase including the light reflecting solid integral particles andimmersed in the second liquid phase in a microfluidic device, whereinthe first liquid phase including the solid parts is fed into a flow of afourth liquid phase not including the second polymerization partnerbefore adding the second polymerization partner to prepare the secondliquid phase including the fourth liquid phase.
 13. The method of claim1, wherein the shell has a thickness of not more than λ; and wherein λis a wavelength of light to be reflected by the light reflecting solidintegral particles.
 14. The method of claim 1, wherein the monodispersespherical microcapsules have a diameter in a range of 10 μm to 200 μm.15. A plurality of monodisperse spherical microcapsules made by themethod of claim 1, wherein each monodisperse spherical microcapsulecomprises: a core; a shell of a polymeric material enclosing the core;and at least one light reflecting solid integral particle reflectingincoming light to be reflected by the at least one solid integralparticle in a defined direction for determining the position andorientation of the microcapsule, embedded in the core and fixed in itsorientation with regard to the shell; wherein the shell and the core aretransparent for the light to be reflected by the at least one lightreflecting solid integral particle entering and exiting themicrocapsule, wherein the shell is so thin that it does essentially notdeflect the light to be reflected by the at least one light reflectingsolid integral particle entering and exiting the microcapsule, andwherein the core includes a main component of the transparent fluid suchthat a refraction index of the core essentially matches a refractionindex of the transparent fluid.
 16. The plurality of monodispersespherical microcapsules of claim 15, wherein the shell has a thicknessof not more than λ; and wherein λ is a wavelength of light to bereflected by the at least one solid integral particle.
 17. The pluralityof monodisperse spherical microcapsules of claim 15, wherein themicrocapsules have a diameter in a range of 10 μm to 200 μm.
 18. Themethod of claim 1, wherein the monodisperse spherical microcapsules havea diameter in a range of 10 μm to 70 μm.
 19. The method of claim 13,wherein the shell has a thickness of not more than λ/2.
 20. Theplurality of monodisperse spherical microcapsules of claim 16, whereinthe shell has a thickness of not more than λ/2.